EP3318569B1 - Bis-phosphites with 2,4-tert. butylphenyl units and their use as ligands in the hydroformylation - Google Patents
Bis-phosphites with 2,4-tert. butylphenyl units and their use as ligands in the hydroformylation Download PDFInfo
- Publication number
- EP3318569B1 EP3318569B1 EP16197715.2A EP16197715A EP3318569B1 EP 3318569 B1 EP3318569 B1 EP 3318569B1 EP 16197715 A EP16197715 A EP 16197715A EP 3318569 B1 EP3318569 B1 EP 3318569B1
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- EP
- European Patent Office
- Prior art keywords
- alkyl
- substituted
- compound according
- substituents
- hydroformylation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 butylphenyl units Chemical group 0.000 title claims description 48
- 238000007037 hydroformylation reaction Methods 0.000 title claims description 23
- 239000003446 ligand Substances 0.000 title description 26
- 150000001875 compounds Chemical class 0.000 claims description 34
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 16
- 150000001336 alkenes Chemical class 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 10
- 125000002252 acyl group Chemical group 0.000 claims description 10
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052703 rhodium Inorganic materials 0.000 claims description 10
- 229910052741 iridium Inorganic materials 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 30
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000010948 rhodium Substances 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 150000001299 aldehydes Chemical class 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- GVQAJJUPWDZQGD-UHFFFAOYSA-N 1-tert-butyl-3-(3-tert-butyl-5-methoxyphenyl)-5-methoxybenzene Chemical compound CC(C)(C)C1=CC(OC)=CC(C=2C=C(C=C(OC)C=2)C(C)(C)C)=C1 GVQAJJUPWDZQGD-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- DQTRYXANLKJLPK-UHFFFAOYSA-N chlorophosphonous acid Chemical compound OP(O)Cl DQTRYXANLKJLPK-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 4
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 0 CC*(C(C)C1CCCCC1)C=* Chemical compound CC*(C(C)C1CCCCC1)C=* 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- 238000010626 work up procedure Methods 0.000 description 3
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- CBYWHFTZNVZQHV-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-4-methoxyphenol Chemical compound CC(C)(C)C1=CC(OC)=CC(C=2C(=C(C=C(OC)C=2)C(C)(C)C)O)=C1O CBYWHFTZNVZQHV-UHFFFAOYSA-N 0.000 description 2
- 241000239290 Araneae Species 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 2
- NCRXKTXSENVLFG-UHFFFAOYSA-N chloro-bis(2,4-dimethylphenoxy)phosphane Chemical compound CC1=CC(C)=CC=C1OP(Cl)OC1=CC=C(C)C=C1C NCRXKTXSENVLFG-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 2
- 239000012045 crude solution Substances 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 235000013847 iso-butane Nutrition 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- VIHUHUGDEZCPDK-GQCTYLIASA-N (e)-5-methylhept-2-ene Chemical compound CCC(C)C\C=C\C VIHUHUGDEZCPDK-GQCTYLIASA-N 0.000 description 1
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical class CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- RCBGGJURENJHKV-UHFFFAOYSA-N 2-methylhept-1-ene Chemical compound CCCCCC(C)=C RCBGGJURENJHKV-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- QDMFTFWKTYXBIW-UHFFFAOYSA-N 3-Methyl-1-heptene Chemical compound CCCCC(C)C=C QDMFTFWKTYXBIW-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XTVRLCUJHGUXCP-UHFFFAOYSA-N 3-methyleneheptane Chemical compound CCCCC(=C)CC XTVRLCUJHGUXCP-UHFFFAOYSA-N 0.000 description 1
- RITONZMLZWYPHW-UHFFFAOYSA-N 3-methylhex-1-ene Chemical class CCCC(C)C=C RITONZMLZWYPHW-UHFFFAOYSA-N 0.000 description 1
- XZJZVNABSFJYOK-UHFFFAOYSA-N 3-methylidenenonane Chemical compound CCCCCCC(=C)CC XZJZVNABSFJYOK-UHFFFAOYSA-N 0.000 description 1
- GLUPFQMLFXGTNL-UHFFFAOYSA-N 3-methyloct-1-ene Chemical class CCCCCC(C)C=C GLUPFQMLFXGTNL-UHFFFAOYSA-N 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- MNVMYTVDDOXZLS-UHFFFAOYSA-N 4-methoxyguaiacol Natural products COC1=CC=C(O)C(OC)=C1 MNVMYTVDDOXZLS-UHFFFAOYSA-N 0.000 description 1
- CZAYAZBUNCPRET-UHFFFAOYSA-N C=CC.C(CCC)C=CC Chemical compound C=CC.C(CCC)C=CC CZAYAZBUNCPRET-UHFFFAOYSA-N 0.000 description 1
- UVSJEAKWFHRUQG-UHFFFAOYSA-N CC(C)(C)c(cc1C(C)(C)C)ccc1OP(Oc1c(C(C)(C)C)cc(C(C)(C)C)cc1)Oc(c(C(C)(C)C)cc(OC)c1)c1-c(cc(cc1C(C)(C)C)OC)c1OP(Oc1c(C(C)(C)C)cc(C(C)(C)C)cc1)Oc1ccc(C(C)(C)C)cc1C(C)(C)C Chemical compound CC(C)(C)c(cc1C(C)(C)C)ccc1OP(Oc1c(C(C)(C)C)cc(C(C)(C)C)cc1)Oc(c(C(C)(C)C)cc(OC)c1)c1-c(cc(cc1C(C)(C)C)OC)c1OP(Oc1c(C(C)(C)C)cc(C(C)(C)C)cc1)Oc1ccc(C(C)(C)C)cc1C(C)(C)C UVSJEAKWFHRUQG-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005669 hydrocyanation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003041 laboratory chemical Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N propyl ethylene Natural products CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/1411—Esters of phosphorous acids with hydroxyalkyl compounds with further substituents on alkyl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
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Definitions
- the invention relates to bisphosphites with 2,4- tert -butylphenyl units and to a process for their preparation. Furthermore, the invention relates to the use of the compounds as ligands in a ligand-metal complex.
- the compound, as well as the complex, can be used as a catalytically active composition in hydroformylation reactions.
- Phosphorus-containing compounds play a crucial role as ligands in a variety of reactions. These include phosphite ligands, ie compounds containing P-O bonds, which find application in hydrogenation, hydrocyanation and especially in hydroformylation.
- symmetrically constructed bisphosphites are prepared and used as ligands for hydroformylation.
- the symmetrically constructed bisphosphite ligands used in the hydroformylation are prepared at low temperatures. Compliance with these low temperatures is imperative because higher temperatures according to these US documents would lead to rearrangements and ultimately to asymmetrically constructed bisphosphites.
- a ligand which gives a very good yield is the ligand according to formula ( 2 ):
- Raffinate 3 is a mixture of: about 26% 1-butene, 32% trans-2-butene, 17% cis-2-butene, 25% n-butane and traces of iso-butane and neo-pentane.
- the regioselectivity with respect to the n-aldehyde means that this amount of linear product was formed. The remaining percentages then correspond to the branched isomer. With a regioselectivity of 50%, n-aldehyde and iso-aldehyde are formed in equal parts.
- - (C 1 -C 12 ) -alkyl comprises straight-chain and branched alkyl groups. Preferably, these are unsubstituted straight-chain or branched - (C 1 -C 8 ) -alkyl and most preferably - (C 1 -C 6 ) -alkyl groups.
- Examples of - (C 1 -C 12 ) -alkyl groups are, in particular, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2- Methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3 Methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethy
- Substituted - (C 1 -C 12 ) -alkyl groups and substituted - (C 1 -C 12 ) -alkoxy groups may, depending on their chain length, have one or more substituents; the Substituents are independently selected from - (C 3 -C 12 ) -cycloalkyl, - (C 3 -C 12 ) -heterocycloalkyl, - (C 6 -C 20 ) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl ,
- R 2 and R 4 are selected from: - (C 1 -C 12 ) alkyl, -O- (C 1 -C 12 ) alkyl.
- R 2 is -O- (C 1 -C 12 ) -alkyl.
- R 4 is - (C 1 -C 12 ) alkyl.
- R 1 , R 2 , R 3 , R 4 are selected from: -H, -Me, -tBu, -OMe, -iPr.
- R 1 is -H.
- R 2 , R 4 are selected from: -Me, -tBu, -OMe, -iPr.
- R 2 , R 4 are selected from: -Me, -tBu, -OMe,
- R 2 is selected from: -Me, -tBu, -OMe.
- R 2 is selected from: -tBu, -OMe.
- R 2 is selected from: -Me, -OMe.
- R 2 is -OMe.
- R 3 is -H.
- R 4 is selected from: -Me, -tBu, -OMe.
- R 4 is selected from: -tBu, -OMe.
- R 4 is selected from -Me, -tBu.
- R 4 is -tBu.
- the compound has the formula ( 1 ):
- M Rh.
- M Rh.
- hydroformylation process is claimed in which the compound ( I ) or the complexes ( II ) or ( III ) is used.
- the compound can be used as a ligand in a ligand-metal complex.
- each ligand is bound in the form of a ligand-metal complex, but is contained as a free ligand in the reaction mixture.
- the reaction is carried out under usual conditions.
- the metal is Rh.
- the educts for the hydroformylation according to the process of the invention are olefins or mixtures of olefins, in particular monoolefins having 2 to 24, preferably 3 to 16, particularly preferably 3 to 12 carbon atoms with terminal or internal CC double bonds, such as 1-propene, 1-butene, 2-butene, 1- or 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, 1, 2 or 3, -hexene, the C 6 olefin mixture (dipropene), heptene, 2- or 3-methyl-1-hexenes, octenes, 2-methylheptene, 3-methylheptene, 5-methyl-2-heptene, 6-methylene obtained in the dimerization of propene 2-heptene, 2-ethyl-1-hexene, the C 8 olefin mixture obtained in the dimerization of butenes (di-n-butene,
- ⁇ -olefins, terminally branched, internally branched and internally branched olefins can be hydroformylated using the ligands according to the invention.
- Nuclear resonance spectra were recorded on Bruker Avance 300 and Bruker Avance 400, gas chromatographic analysis on Agilent GC 7890A, elemental analysis on Leco TruSpec CHNS and Varian ICP-OES 715, and ESI-TOF mass spectrometry on Thermo Electron Finnigan MAT 95-XP and Agilent 6890 N / 5973 devices.
- the resulting hydrochloride was filtered off and rinsed with 60 ml of dried toluene and the resulting mother liquor was concentrated to dryness under reduced pressure.
- the crude solution was distilled.
- a pointed piston was filled with the crude solution, followed by a short distillation bridge without cooling jacket.
- the thermometer was placed at the upper opening and at the other end a spider was attached with four more pointed rams.
- this apparatus was equipped with a cold trap connected and from there with the high vacuum pump.
- the pointed flask with the crude ligand to be distilled was heated by means of an oil bath. First, the flow was removed at a head temperature of 25-30 ° C. Subsequently, the spider was rotated further and at a head temperature of 140 ° C, the main run was removed. When there were no more drops in the main run, the distillation was stopped, the pump was run down and the main run was taken out in the appropriate pointed flask, sealed and analyzed.
- the specified chlorine contents are total chlorine contents.
- the total chlorine content is determined according to Wickbold: Sample preparation according to DIN 51408 and measurement by ion chromatography according to DIN EN ISO 10304.
- Triehtylaminhydrochlorid was filtered off and washed with 20 ml of dried toluene, the filtrate was concentrated to dryness under reduced pressure.
- the biphenol / DMAB solution was then added dropwise at 0 ° C. to the chlorophosphite solution over the course of 1 h. It was then warmed to room temperature overnight and then stirred for 12 hours at 55 ° C. Subsequently, the reaction solution was cooled again to room temperature and filtered off. The solid was washed twice with 20 ml each of dried acetonitrile and then dried under reduced pressure and analyzed.
- the solid was transferred from the frit in a 500 ml Schlenk flask and 400 ml of dried acetonitrile were added. Subsequently, the Schlenk flask was heated to 60 ° C for 5 h, filtered hot and washed once with 20 ml of dried acetonitrile.
- the filtrate was concentrated under reduced pressure and analyzed.
- the Schlenk flask was treated with 80 ml of dried acetonitrile and the suspension was heated to 60 ° C. for 1.5 h and then hot-fritted. Thereafter, the filtrate was concentrated under reduced pressure.
- the solid was dissolved in 20 mL of dried toluene, stirred for 1/2 h at room temperature and then filtered. The solid was washed twice with 10 ml of dried toluene. Then the filtrate is concentrated by means of reduced pressure and analyzed.
- Raffinate 3 is a mixture of: about 26% 1-butene, 32% trans-2-butene, 17% cis-2-butene, 25% n-butane and traces of iso-butane and neo-pentane.
- the precursors were Rh (acac) (CO) 2 in toluene.
- the ligand was used in molar excesses of 4: 1 relative to the rhodium.
- the stabilizer used was Tinuvin 770DF in a molar ratio of about 1: 1 to the ligand.
- TIPB tetraisopropylbenzene
- raffinate 3 In a 100 ml autoclave from Parr Instruments, 8.8 g of raffinate 3 were hydroformylated at 128 ° C. and 43 bar synthesis gas pressure. The precursors were Rh (acac) (CO) 2 (100 ppm Rh) in 45 g of toluene. The ligand used was 0.107 g of ligand in the catalyst feed solution. As organic amine, 0.057 g of Tinuvin 770DF and 0.451 g of TIPB as GC standard were added. The educt was metered in after reaching the intended reaction temperature.
- Table 1 shows the hydroformylation results of raffinate 3 at 43 bar synthesis gas pressure and 128 ° C. ⁇ u> Table 1: ⁇ / u> entry ligand Yield aldehyde in [%] Regioselectivity n-pentanal in% 1 1* 82 43 2 2 54 99 * Inventive compound
- the regioselectivity with respect to the n-aldehyde means that this amount of linear product was formed. The remaining percentages then correspond to the branched isomer. With a regioselectivity of 50%, n-aldehyde and iso-aldehyde are formed in equal parts.
- the regioselectivity in comparison with the comparison ligand ( 2 ) could be clearly approached the 50% mark, which stands for a balanced ratio of n-aldehyde and iso-aldehyde.
Description
Die Erfindung betrifft Bisphosphite mit 2,4-tert.-Butylphenyl-Einheiten und ein Verfahren zu deren Herstellung. Des Weiteren betrifft die Erfindung die Verwendung der Verbindungen als Liganden in einem Ligand-Metall-Komplex. Die Verbindung, wie auch der Komplex, können als katalytisch aktive Zusammensetzung in Hydroformylierungsreaktionen eingesetzt werden.The invention relates to bisphosphites with 2,4- tert -butylphenyl units and to a process for their preparation. Furthermore, the invention relates to the use of the compounds as ligands in a ligand-metal complex. The compound, as well as the complex, can be used as a catalytically active composition in hydroformylation reactions.
Phosphorhaltige Verbindungen spielen als Liganden in einer Vielzahl von Reaktionen eine entscheidende Rolle. Hierzu zählen Phosphitliganden, also Verbindungen, die P-O-Bindungen enthalten, die in der Hydrierung, Hydrocyanierung und vor allem in der Hydroformylierung Anwendung finden.Phosphorus-containing compounds play a crucial role as ligands in a variety of reactions. These include phosphite ligands, ie compounds containing P-O bonds, which find application in hydrogenation, hydrocyanation and especially in hydroformylation.
Die Reaktionen zwischen Olefinverbindungen, Kohlenmonoxid und Wasserstoff in Gegenwart eines Katalysators zu den um ein C-Atom reicheren Aldehyden ist als Hydroformylierung bzw. Oxierung bekannt. Als Katalysatoren in diesen Reaktionen werden häufig Verbindungen der Übergangsmetalle der VIII. Gruppe des Periodensystems der Elemente verwendet. Bekannte Liganden sind beispielsweise Verbindungen aus den Klassen der Phosphine, Phosphite und Phosphonite mit jeweils dreiwertigen Phosphor PIII. Eine gute Übersicht über den Stand der Hydroformylierung von Olefinen findet sich in
Literaturbekannt ist die Synthese symmetrisch aufgebauter Bisphosphite, wie sie beispielsweise in
In
Ein Ligand, welcher eine sehr gute Ausbeute liefert, ist der Ligand gemäß Formel (2):
Bei der Hydroformylierung von Raffinat 3 liefert der Ligand (2) allerdings fast ausschließlich (zu 99%) das n-Pentanal. Raffinat 3 ist ein Gemisch aus: ca. 26% 1-Buten, 32% trans-2-Buten, 17% cis-2-Buten, 25% n-Butan und Spuren an Iso-Butan und Neo-Pentan.In the hydroformylation of raffinate 3, however, the ligand ( 2 ) gives almost exclusively (99%) the n-pentanal. Raffinate 3 is a mixture of: about 26% 1-butene, 32% trans-2-butene, 17% cis-2-butene, 25% n-butane and traces of iso-butane and neo-pentane.
Für manche technischen Anwendungen ist es aber erstrebenswert, dass das Verhältnis von Linearem Aldehyd (= n-Aldehyd) zu verzweigtem Aldehyd (= iso-Aldehyd) möglichst ausgeglichen ist.For some technical applications, however, it is desirable that the ratio of linear aldehyde (= n-aldehyde) to branched aldehyde (= iso-aldehyde) is as balanced as possible.
Bei der Hydroformylierung gibt es die n/iso-Selektivitäte: das Verhältnis von linearem Aldehyd (= n) zu verzweigtem Aldehyd (= iso). Hierbei bedeutet die Regioselektivität bezüglich des n-Aldehyden, dass diese Menge an linearem Produkt gebildet wurde. Die restlichen Prozente entsprechen dann dem verzweigten Isomer. Bei einer Regioselektivität von 50% entstehen also n-Aldehyd und iso-Aldehyd zu gleichen Teilen.In the hydroformylation there is the n / iso-selectivity: the ratio of linear aldehyde (= n) to branched aldehyde (= iso). Here, the regioselectivity with respect to the n-aldehyde means that this amount of linear product was formed. The remaining percentages then correspond to the branched isomer. With a regioselectivity of 50%, n-aldehyde and iso-aldehyde are formed in equal parts.
Die technische Aufgabe der Erfindung ist die Bereitstellung eines neuen Liganden, welcher in der Hydroformylierung von ungesättigten Verbindungen nicht die aus dem Stand der Technik zuvor aufgezeigten Nachteile, sondern die folgenden Eigenschaften aufweist:
- 1) eine gute Aktivität/Ausbeute,
- 2) eine n-Regioseliktivität in Bezug auf die Hydroformylierung von 50% +/- 15%.
- 1) good activity / yield,
- 2) an n-regioseliivity with respect to hydroformylation of 50% +/- 15%.
Die Aufgabe wird gelöst durch eine Verbindung gemäß Anspruch 1.The object is achieved by a compound according to claim 1.
- R1, R2, R3, R4 ausgewählt sind aus: -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl,
- wobei die genannten Alkylgruppen wie folgt substituiert sein können:
substituierte -(C1-C12)-Alkylgruppen und substituierte -(C1-C12)-Alkoxygruppen können in Abhängigkeit von ihrer Kettenlänge, einen oder mehrere Substituenten aufweisen; die Substituenten sind unabhängig voneinander ausgewählt unter -(C3-C12)-Cycloalkyl, -(C3-C12)-Heterocycloalkyl, -(C6-C20)-Aryl, Fluor, Chlor, Cyano, Formyl, Acyl oder Alkoxycarbonyl, wobei mindestens einer der Reste R1,R2,R3,R4 nicht für -H steht.
- R 1 , R 2 , R 3 , R 4 are selected from: -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl,
- wherein said alkyl groups may be substituted as follows:
substituted - (C 1 -C 12 ) -alkyl groups and substituted - (C 1 -C 12 ) -alkoxy groups may, depending on their chain length, have one or more substituents; the substituents are independently selected from - (C 3 -C 12 ) -cycloalkyl, - (C 3 -C 12 ) -heterocycloalkyl, - (C 6 -C 20 ) -aryl, fluorine, chlorine, cyano, formyl, acyl or Alkoxycarbonyl, wherein at least one of the radicals R 1 , R 2 , R 3 , R 4 is not -H.
Im Rahmen der Erfindung umfasst der Ausdruck -(C1-C12)-Alkyl geradkettige und verzweigte Alkylgruppen. Vorzugsweise handelt es sich dabei um unsubstituierte geradkettige oder verzweigte -(C1-C8)-Alkyl- und ganz bevorzugt -(C1-C6)-Alkylgruppen. Beispiele für -(C1-C12)-Alkylgruppen sind insbesondere Methyl, Ethyl, Propyl, Isopropyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, 2-Pentyl, 2-Methylbutyl-, 3-Methylbutyl-, 1,2-Dimethylpropyl-, 1,1-Dimethylpropyl, 2,2-Dimethylpropyl-, 1-Ethylpropyl-, n-Hexyl-, 2-Hexyl-, 2-Methylpentyl-, 3-Methylpentyl-, 4-Methylpentyl-, 1,1-Dimethylbutyl-, 1,2-Diemthylbutyl-, 2,2-Dimethylbutyl-, 1,3-Dimethylbutyl-, 2,3-Dimethylbutyl-, 3,3-Dimethylbutyl-, 1,1,2-Trimethylpropyl-, 1,2,2-Trimethylpropyl-, 1-Ethylbutyl-, 1-Ethyl-2-methylpropyl-, n-Heptyl-, 2-Heptyl-, 3-Heptyl-, 2-Ethylpentyl-, 1-Propylbutyl-, n-Octyl-, 2-Ethylhexyl-, 2-Propylheptyl-, Nonyl-, Decyl.In the context of the invention, the term - (C 1 -C 12 ) -alkyl comprises straight-chain and branched alkyl groups. Preferably, these are unsubstituted straight-chain or branched - (C 1 -C 8 ) -alkyl and most preferably - (C 1 -C 6 ) -alkyl groups. Examples of - (C 1 -C 12 ) -alkyl groups are, in particular, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2- Methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3 Methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl -, 1-Propylbutyl, n-octyl, 2-ethylhexyl, 2-propylheptyl, nonyl, decyl.
Die Erläuterungen zum Ausdruck -(C1-C12)-Alkyl gelten auch für die Alkylgruppen in -O-(C1-C12)-Alkyl, also in -(C1-C12)-Alkoxy. Vorzugsweise handelt es sich dabei um unsubstituierte geradkettige oder verzweigte -(C1-C6)-Alkoxygruppen.The explanations concerning the expression - (C 1 -C 12 ) -alkyl also apply to the alkyl groups in -O- (C 1 -C 12 ) -alkyl, ie in - (C 1 -C 12 ) -alkoxy. These are preferably unsubstituted straight-chain or branched - (C 1 -C 6 ) -alkoxy groups.
Substituierte -(C1-C12)-Alkylgruppen und substituierte -(C1-C12)-Alkoxygruppen können in Abhängigkeit von ihrer Kettenlänge, einen oder mehrere Substituenten aufweisen; die Substituenten sind unabhängig voneinander ausgewählt unter -(C3-C12)-Cycloalkyl, -(C3-C12)-Heterocycloalkyl, -(C6-C20)-Aryl, Fluor, Chlor, Cyano, Formyl, Acyl oder Alkoxycarbonyl.Substituted - (C 1 -C 12 ) -alkyl groups and substituted - (C 1 -C 12 ) -alkoxy groups may, depending on their chain length, have one or more substituents; the Substituents are independently selected from - (C 3 -C 12 ) -cycloalkyl, - (C 3 -C 12 ) -heterocycloalkyl, - (C 6 -C 20 ) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl ,
In einer Ausführungsform sind R2 und R4 ausgewählt aus: -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl.In one embodiment, R 2 and R 4 are selected from: - (C 1 -C 12 ) alkyl, -O- (C 1 -C 12 ) alkyl.
In einer Ausführungsform steht R2 für -O-(C1-C12)-Alkyl.In one embodiment, R 2 is -O- (C 1 -C 12 ) -alkyl.
In einer Ausführungsform steht R4 für -(C1-C12)-Alkyl.In one embodiment, R 4 is - (C 1 -C 12 ) alkyl.
In einer Ausführungsform sind R1, R2, R3, R4 ausgewählt aus: -H, -Me, -tBu, -OMe, -iPr.In one embodiment, R 1 , R 2 , R 3 , R 4 are selected from: -H, -Me, -tBu, -OMe, -iPr.
In einer Ausführungsform steht R1 für -H.In one embodiment, R 1 is -H.
In einer Ausführungsform sind R2, R4 ausgewählt aus: -Me, -tBu, -OMe, -iPr.In one embodiment, R 2 , R 4 are selected from: -Me, -tBu, -OMe, -iPr.
In einer Ausführungsform sind R2, R4 ausgewählt aus: -Me, -tBu, -OMe,In one embodiment, R 2 , R 4 are selected from: -Me, -tBu, -OMe,
In einer Ausführungsform ist R2 ausgewählt aus: -Me, -tBu, -OMe.In one embodiment, R 2 is selected from: -Me, -tBu, -OMe.
In einer Ausführungsform ist R2 ausgewählt aus: -tBu, -OMe.In one embodiment, R 2 is selected from: -tBu, -OMe.
In einer Ausführungsform ist R2 ausgewählt aus: -Me, -OMe.In one embodiment, R 2 is selected from: -Me, -OMe.
In einer Ausführungsform steht R2 für -OMe.In one embodiment, R 2 is -OMe.
In einer Ausführungsform steht R3 für -H.In one embodiment, R 3 is -H.
In einer Ausführungsform ist R4 ausgewählt aus: -Me, -tBu, -OMe.In one embodiment, R 4 is selected from: -Me, -tBu, -OMe.
In einer Ausführungsform ist R4 ausgewählt aus: -tBu, -OMe.In one embodiment, R 4 is selected from: -tBu, -OMe.
In einer Ausführungsform ist R4 ausgewählt aus: -Me, -tBu.In one embodiment, R 4 is selected from -Me, -tBu.
In einer Ausführungsform steht R4 für -tBu.In one embodiment, R 4 is -tBu.
In einer Ausführungsform weist die Verbindung die Formel (1) auf:
Neben den Verbindungen werden auch Komplexe beansprucht, welche die Verbindung umfassen.In addition to the compounds, complexes which comprise the compound are also claimed.
- R1, R2, R3, R4 ausgewählt sind aus: -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl,
- wobei die genannten Alkylgruppen wie folgt substituiert sein können:
- substituierte -(C1-C12)-Alkylgruppen und substituierte -(C1-C12)-Alkoxygruppen können in Abhängigkeit von ihrer Kettenlänge, einen oder mehrere Substituenten aufweisen; die Substituenten sind unabhängig voneinander ausgewählt unter -(C3-C12)-Cycloalkyl, -(C3-C12)-Heterocycloalkyl, -(C6-C20)-Aryl, Fluor, Chlor, Cyano, Formyl, Acyl oder Alkoxycarbonyl;
- und M ausgewählt ist aus: Rh, Ru, Co, Ir.
- R 1 , R 2 , R 3 , R 4 are selected from: -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl,
- wherein said alkyl groups may be substituted as follows:
- substituted - (C 1 -C 12 ) -alkyl groups and substituted - (C 1 -C 12 ) -alkoxy groups may, depending on their chain length, have one or more substituents; the substituents are independently selected from - (C 3 -C 12 ) -cycloalkyl, - (C 3 -C 12 ) -heterocycloalkyl, - (C 6 -C 20 ) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl;
- and M is selected from: Rh, Ru, Co, Ir.
In einer bevorzugten Ausführungsform ist M = Rh.In a preferred embodiment, M = Rh.
Die in Zusammenhang mit der Formel (I) oben angeführten Ausführungsformen und Auswahlmöglichkeiten für die Reste R1, R2, R3, R4 gelten analog für die Formel (II).The embodiments and possible choices for the radicals R 1 , R 2 , R 3 , R 4 mentioned above in connection with the formula ( I ) apply analogously to the formula ( II ).
- R1, R2, R3, R4 ausgewählt sind aus: -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl,
- wobei die genannten Alkylgruppen wie folgt substituiert sein können:
- substituierte -(C1-C12)-Alkylgruppen und substituierte -(C1-C12)-Alkoxygruppen können in Abhängigkeit von ihrer Kettenlänge, einen oder mehrere Substituenten aufweisen; die Substituenten sind unabhängig voneinander ausgewählt unter -(C3-C12)-Cycloalkyl, -(C3-C12)-Heterocycloalkyl, -(C6-C20)-Aryl, Fluor, Chlor, Cyano, Formyl, Acyl oder Alkoxycarbonyl;
- und M ausgewählt ist aus: Rh, Ru, Co, Ir.
- R 1 , R 2 , R 3 , R 4 are selected from: -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl,
- wherein said alkyl groups may be substituted as follows:
- substituted - (C 1 -C 12 ) -alkyl groups and substituted - (C 1 -C 12 ) -alkoxy groups may, depending on their chain length, have one or more substituents; the substituents are independently selected from - (C 3 -C 12 ) -cycloalkyl, - (C 3 -C 12 ) -heterocycloalkyl, - (C 6 -C 20 ) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl;
- and M is selected from: Rh, Ru, Co, Ir.
In einer bevorzugten Ausführungsform ist M = Rh.In a preferred embodiment, M = Rh.
Die in Zusammenhang mit der Formel (I) oben angeführten Ausführungsformen und Auswahlmöglichkeiten für die Reste R1, R2, R3, R4 gelten analog für die Formel (III).The embodiments and selection possibilities for the radicals R 1 , R 2 , R 3 , R 4 mentioned above in connection with the formula ( I ) apply analogously to the formula ( III ).
Neben der Verbindung und den Komplexen, welche die Verbindung umfassen, wird auch die Verwendung der Verbindung (I) beziehungsweise der Komplexe (II) oder (III) zur Katalyse einer Hydroformylierungsreaktion beansprucht.In addition to the compound and the complexes comprising the compound, the use of the compound ( I ) or the complexes ( II ) or ( III ) for catalyzing a hydroformylation reaction is also claimed.
Verwendung der Verbindung (I) in einem Ligand-Metall-Komplex zur Katalyse einer Hydroformylierungsreaktion.Use of compound ( I ) in a ligand-metal complex to catalyze a hydroformylation reaction.
Verwendung des Komplexes (II) zur Katalyse einer Hydroformylierungsreaktion.Use of the complex ( II ) for catalyzing a hydroformylation reaction.
Verwendung des Komplexes (III) zur Katalyse einer Hydroformylierungsreaktion.Use of the complex ( III ) to catalyze a hydroformylation reaction.
Des Weiteren wird auch das Hydroformylierungsverfahren beansprucht, in welchem die Verbindung (I) beziehungsweise der Komplexe (II) oder (III) zum Einsatz kommt.Furthermore, the hydroformylation process is claimed in which the compound ( I ) or the complexes ( II ) or ( III ) is used.
Verfahren umfassend die Verfahrensschritte:
- a) Vorlegen eines Olefins,
- b) Zugabe eines zuvor beschriebenen Komplexes,
oder einer zuvor beschriebenen Verbindung und einer Substanz, welche ein Metall ausgewählt aus: Rh, Ru, Co, Ir aufweist, - c) Zuführen von H2 und CO,
- d) Erwärmen des Reaktionsgemisches, wobei das Olefin zu einem Aldehyd umgesetzt wird.
- a) presentation of an olefin,
- b) addition of a complex described above,
or a compound described above and a substance which has a metal selected from: Rh, Ru, Co, Ir, - c) supplying H 2 and CO,
- d) heating the reaction mixture, wherein the olefin is reacted to an aldehyde.
Die Verfahrensschritte a) bis c) können hierbei in beliebiger Reihenfolge erfolgen.The process steps a) to c) can be carried out in any order.
Die Verbindung kann als Ligand in einem Ligand-Metall-Komplex eingesetzt werden.The compound can be used as a ligand in a ligand-metal complex.
Es kann hierbei auch ein Überschuss an Liganden verwendet werden und nicht zwangsläufig jeder Ligand liegt gebunden in Form eines Ligand-Metall-Komplexes vor, sondern ist als freier Ligand im Reaktionsgemisch enthalten.It is also possible here to use an excess of ligands and not necessarily each ligand is bound in the form of a ligand-metal complex, but is contained as a free ligand in the reaction mixture.
Die Reaktion wird bei üblichen Bedingungen durchgeführt.The reaction is carried out under usual conditions.
Bevorzugt sind eine Temperatur von 80 °C bis 160 °C und ein Druck von 1 bis 300 bar. Besonders bevorzugt sind eine Temperatur von 100 °C bis 160 °C und ein Druck von 15 bis 250 bar.Preferred are a temperature of 80 ° C to 160 ° C and a pressure of 1 to 300 bar. Particularly preferred are a temperature of 100 ° C to 160 ° C and a pressure of 15 to 250 bar.
In einer bevorzugten Ausführungsform ist das Metall Rh.In a preferred embodiment, the metal is Rh.
Die Edukte für die Hydroformylierung gemäß dem Verfahren der Erfindung sind Olefine oder Gemische von Olefinen, insbesondere Monoolefine mit 2 bis 24, bevorzugt 3 bis 16, besonders bevorzugt 3 bis 12 Kohlenstoffatomen mit end- oder innenständigen C-C-Doppelbindungen, wie z.B. 1-Propen, 1-Buten, 2-Buten, 1- oder 2-Penten, 2-Methyl-1-buten, 2-Methyl-2-buten, 3-Methyl-1-buten, 1-, 2- oder 3,-Hexen, das bei der Dimerisierung von Propen anfallende C6-Olefingemisch (Dipropen), Heptene, 2- oder 3-Methyl-1-hexene, Octene, 2-Methylheptene, 3-Methylheptene, 5-Methyl-2-hepten, 6-Methyl-2-hepten, 2-Ethyl-1-hexen, das bei der Dimerisierung von Butenen anfallende C8-Olefingemisch (Di-n-buten, Di-iso-buten), Nonene, 2- oder 3-Methyloctene, das bei der Trimerisierung von Propen anfallende C9-Olefingemisch (Tripropen), Decene, 2-Ethyl-1-octen, Dodecene, das bei der Tetramerisierung von Propen oder der Trimerisierung von Butenen anfallende C12-Olefingemisch (Tetrapropen oder Tributen), Tetradecene, Hexadecene, das bei der Tetramerisierung von Butenen anfallende C16-Olefingemisch (Tetrabuten) sowie durch Cooligomerisierung von Olefinen mit unterschiedlicher Anzahl von Kohlenstoffatomen (bevorzugt 2 bis 4) hergestellte Olefingemische.The educts for the hydroformylation according to the process of the invention are olefins or mixtures of olefins, in particular monoolefins having 2 to 24, preferably 3 to 16, particularly preferably 3 to 12 carbon atoms with terminal or internal CC double bonds, such as 1-propene, 1-butene, 2-butene, 1- or 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, 1, 2 or 3, -hexene, the C 6 olefin mixture (dipropene), heptene, 2- or 3-methyl-1-hexenes, octenes, 2-methylheptene, 3-methylheptene, 5-methyl-2-heptene, 6-methylene obtained in the dimerization of propene 2-heptene, 2-ethyl-1-hexene, the C 8 olefin mixture obtained in the dimerization of butenes (di-n-butene, di-isobutene), nonenes, 2- or 3-methyl-octenes the trimerization of propene resulting C 9 olefin mixture (tripropene), decene, 2-ethyl-1-octene, dodecenes, the resulting in the tetramerization of propene or the trimerization of butenes C 12 -Olefingemisch (tetrapropene or tributene), tetradecenes, hexadecenes , the C 16 -olefin mixture (tetrabutene) obtained in the tetramerization of butenes and olefin mixtures prepared by co-oligomerization of olefins with different numbers of carbon atoms (preferably 2 to 4).
Mit dem erfindungsgemäßen Verfahren können unter Verwendung der erfindungsgemäßen Liganden α-Olefine, endständig verzweigte, innenständige und innenständig verzweigte Olefine hydroformyliert werden.With the process according to the invention, α-olefins, terminally branched, internally branched and internally branched olefins can be hydroformylated using the ligands according to the invention.
Im Folgenden soll die Erfindung anhand von Ausführungsbeispielen näher erläutert werden.In the following, the invention will be explained in more detail with reference to exemplary embodiments.
Alle nachfolgenden Präparationen wurden mit Standard-Schlenk-Technik unter Schutzgas durchgeführt. Die Lösungsmittel wurden vor Gebrauch über geeigneten Trocknungsmitteln getrocknet (
Phosphortrichlorid (Aldrich) wurde vor dem Einsatz unter Argon destilliert. Alle präparativen Arbeiten erfolgten in ausgeheizten Gefäßen. Die Charakterisierung der Produkte erfolgte mittels NMR-Spektroskopie. Chemische Verschiebungen (δ) werden in ppm angegeben. Die Referenzierung der 31P-NMR-Signale erfolgte gemäß: SR31P = SR1H ∗ (BF31P / BF1H) = SR1H ∗ 0,4048. (
Die Aufnahme von Kernresonanzspektren erfolgte an Bruker Avance 300 bzw. Bruker Avance 400, die gaschromatografische Analyse an Agilent GC 7890A, die Elementaranalyse an Leco TruSpec CHNS und Varian ICP-OES 715, und die ESI-TOF Massenspektrometrie an Thermo Electron Finnigan MAT 95-XP und Agilent 6890 N/5973 Geräten.Nuclear resonance spectra were recorded on Bruker Avance 300 and Bruker Avance 400, gas chromatographic analysis on Agilent GC 7890A, elemental analysis on Leco TruSpec CHNS and Varian ICP-OES 715, and ESI-TOF mass spectrometry on Thermo Electron Finnigan MAT 95-XP and Agilent 6890 N / 5973 devices.
In einem sekurierten 1200 ml Glasreaktor, mit Tropftrichter versehen, wurden 50 g PCl3 (0.363 mol) und 86 g Pyridin (1.076 mol) in 380 ml getrocknetem Toluol vorgelegt. Die milchig-gelbe PCl3/Pyridin-Lösung wurde unter Rühren auf -7 °C heruntergekühlt. Dann wurde in den Tropftrichter 86 ml 2,4-Dimethylphenol (0.720 mol) hinzugegeben und in 380 ml getrocknetem Toluol gelöst. Zur Durchführung wurde die Phenol/Toluol-Lösung langsam und stetig zur PCl3/Pyridin-Lösung hinzugetropft. Über Nacht wurde die Reaktionsmischung unter Rühren auf Raumtemperatur gebracht.In a seked 1200 ml glass reactor, provided with dropping funnel, 50 g of PCl 3 (0.363 mol) and 86 g of pyridine (1.076 mol) were placed in 380 ml of dried toluene. The milky-yellow PCl 3 / pyridine solution was cooled down to -7 ° C. with stirring. Then 86 ml of 2,4-dimethylphenol (0.720 mol) was added to the dropping funnel and dissolved in 380 ml of dried toluene. To carry out the phenol / toluene solution was slowly and steadily added dropwise to PCl 3 / pyridine solution. The reaction mixture was brought to room temperature overnight with stirring.
Zur Aufarbeitung wurde das entstandene Hydrochlorid abfiltriert und mit 60 ml getrocknetem Toluol nachgespült und die entstandene Mutterlauge unter vermindertem Druck bis zur Trockne eingeengt.For workup, the resulting hydrochloride was filtered off and rinsed with 60 ml of dried toluene and the resulting mother liquor was concentrated to dryness under reduced pressure.
Zur weiteren Aufarbeitung wurde die Rohlösung destilliert. Hierfür wurde ein Spitzkolben mit der Rohlösung befüllt, darauf kam eine kurze Destillationsbrücke ohne Kühlmantel. An der oberen Öffnung wurde das Thermometer platziert, am anderen Ende wurde eine Spinne mit vier weiteren Spitzkolben befestigt. Anschließend wurde diese Apparatur mit einer Kühlfalle verbunden und von dort aus mit der Hochvakuumpumpe. Der Spitzkolben mit dem zu destillierenden Rohliganden wurde mittels Ölbad erwärmt. Zuerst wurde der Vorlauf bei einer Kopftemperatur von 25-30 °C abgenommen. Anschließend wurde die Spinne weiter gedreht und bei einer Kopftemperatur von 140 °C wurde der Hauptlauf abgenommen. Als keine Tropfen mehr im Hauptlauf ankamen, wurde die Destillation abgestellt, die Pumpe runtergefahren und der Hauptlauf in dem entsprechenden Spitzkolben entnommen, verschlossen und analysiert.For further workup, the crude solution was distilled. For this purpose, a pointed piston was filled with the crude solution, followed by a short distillation bridge without cooling jacket. The thermometer was placed at the upper opening and at the other end a spider was attached with four more pointed rams. Subsequently, this apparatus was equipped with a cold trap connected and from there with the high vacuum pump. The pointed flask with the crude ligand to be distilled was heated by means of an oil bath. First, the flow was removed at a head temperature of 25-30 ° C. Subsequently, the spider was rotated further and at a head temperature of 140 ° C, the main run was removed. When there were no more drops in the main run, the distillation was stopped, the pump was run down and the main run was taken out in the appropriate pointed flask, sealed and analyzed.
Gesamtmasse: 56.7 g (46% Ausbeute)Total mass: 56.7 g (46% yield)
In einem 1000 mL Schlenkkolben wurden zu 51,86 g (0,153 mol) Bis-(2,4-dimethylphenyl)-chlorophosphit unter Rühren bei Raumtemperatur 260 ml getrocknetem Acetonitril zugegeben und das Chlorophosphit aufgelöst.260 ml of dried acetonitrile were added to 51.86 g (0.153 mol) of bis (2,4-dimethylphenyl) chlorophosphite in a 1000 ml Schlenk flask while stirring at room temperature, and the chlorophosphite was dissolved.
In einen zweiten 250 ml Schlenkkolben wurden 20,1 g (0,056 mol) 3,3'-Di-tert.-butyl-5,5'-dimethoxy-[1,1'-biphenyl]-2,2'diol mit 12,4 ml (0,153 mol) Pyridin und 155 ml getrocknetem Acetonitril versetzt. Nun wurde die Chlorophosphitlösung im Schlenkkolben auf 0 °C abgekühlt. Anschließend wurde langsam unter kräftigem Rühren die Biphenol/Pyridin-Lösung zugetropft. Die Reaktionsmischung wurde ca. 3 h bei dieser Temperatur gehalten und dann ganz langsam über Nacht auf Raumtemperatur gebracht.In a second 250 ml Schlenk flask were 20.1 g (0.056 mol) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'-biphenyl] -2,2'diol with 12 , 4 ml (0.153 mol) of pyridine and 155 ml of dried acetonitrile. The chlorophosphite solution was then cooled to 0 ° C. in a Schlenk flask. Subsequently, the biphenol / pyridine solution was slowly added dropwise with vigorous stirring. The reaction mixture was held at this temperature for about 3 hours and then brought to room temperature very slowly overnight.
Dann wurde die Suspension abfiltriert, mit 30 ml Acetonitril gut nachgewaschen und getrocknet.Then the suspension was filtered off, washed well with 30 ml of acetonitrile and dried.
Masse: 44,01 g (Ausbeute: 85%)Mass: 44.01 g (yield: 85%)
Um in diesem Rohliganden den Chlorgehalt zu senken wurde dieser aufgereinigt.To reduce the chlorine content in this crude ligand, this was purified.
Die angegebenen Chlorgehalte verstehen sich als Gesamtchlorgehalte.The specified chlorine contents are total chlorine contents.
Der Gesamtchlorgehalt wird nach Wickbold bestimmt: Probenvorbereitung nach DIN 51408 und Messung per lonenchromatographie nach DIN EN ISO 10304.The total chlorine content is determined according to Wickbold: Sample preparation according to DIN 51408 and measurement by ion chromatography according to DIN EN ISO 10304.
Es wurden 5,15 g 3,3'-di-tert-butyl-5,5'-dimethoxy-[1,1'-biphenyl]-2,2'-diyltetrakis(2,4-dimethylphenyl)bis(phosphite) in einen 250 ml Schlenkkolben mit 15 ml entgastem Toluol und 5 ml Pyridin bei 100 °C zum Rühren gebracht bis alles aufgelöst war. Nachdem alles gelöst war wurde noch für weitere 15 min die Temperatur gehalten und dann auf 90 °C abgekühlt.There was added 5.15 g of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'-biphenyl] -2,2'-diyltetrakis (2,4-dimethylphenyl) bis (phosphite) in a 250 ml Schlenk flask with 15 ml of degassed toluene and 5 ml of pyridine at 100 ° C for stirring until everything was dissolved. After all was dissolved, the temperature was maintained for an additional 15 minutes and then cooled to 90 ° C.
In der Zwischenzeit wurde in einen weiteren 250 ml Schlenkkolben 100 ml Heptan und 5ml Pyridin gegeben und die Lösung wurde auf 0 °C herunter gekühlt. Anschließend wurde die Lösung mit dem 3,3'-di-tert-butyl-5,5'-dimethoxy-[1,1'-biphenyl]-2,2'-diyltetrakis(2,4-dimethylphenyl)bis(phosphite) über die Fritte in die kalte Heptan/Pyridin Lösung gegeben und für 3 h bei 0 °C gerührt. Auch hierbei fiel nichts aus. Also wurde auch hier mittels Vakuumpumpe das Lösemittel abgezogen bis der Feststoff ausgefallen und getrocknet war. Anschließend wurden auf den getrockneten Feststoff 50 ml Acetonitril gegeben. Diese Suspension wurde über zwei Tage bei Raumtemperatur gerührt, abgefrittet und mittels Vakuumpumpe getrocknet.In the meantime, 100 ml of heptane and 5 ml of pyridine were added to another 250 ml Schlenk flask and the solution was cooled to 0 ° C. The solution was then treated with 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'-biphenyl] -2,2'-diyltetrakis (2,4-dimethylphenyl) bis (phosphite). added via the frit in the cold heptane / pyridine solution and stirred for 3 h at 0 ° C. Again, nothing turned out. So here too, the solvent was removed by means of a vacuum pump until the solid had precipitated and dried. Subsequently, 50 ml of acetonitrile were added to the dried solid. This suspension was stirred for two days at room temperature, taped off and dried by means of a vacuum pump.
Masse: 3,7 g
Chlorbestimmung: 20/20 ppmMass: 3.7 g
Chlorine determination: 20/20 ppm
In einem sekurierten 2000 ml Schlenkkolben, mit Trofptrichter versehen, wurden 240 ml getrocknetes Toluol und 8,8 ml Phosphortrichlorid vorgelegt und unter Rühren auf 0 °C abgekühlt.240 ml of dried toluene and 8.8 ml of phosphorus trichloride were introduced into a seked 2000 ml Schlenk flask equipped with a funnel and cooled to 0 ° C. with stirring.
In einem zweiten 1000 ml Schlenkkolben wurden 41,6 g 2,4-Di-tert.-Butylphenol abgewogen, in 415 ml getrocknetem Toluol gelöst und mit 100 ml Triethylamin versetzt.In a second 1000 ml Schlenk flask 41.6 g of 2,4-di-tert-butylphenol were weighed, dissolved in 415 ml of dried toluene and treated with 100 ml of triethylamine.
Dann wurde die Phenol/Triethylamin-Lösung in den Tropftrichter überführt. Nun wurde unter kräftigem Rühren innerhalb von 4h die Phenol/Triethylamin-Lösung zur gut gekühlten Toluol/Phosphortrichlorid-Lösung getropft. Dabei wurde auf eine konstante Tropfgeschwindigkeit von einem Tropfen pro Sekunde geachtet. Anschließend wurde die Mischung auf Raumtemperatur erwärmt und 12 Stunden gerührt, danach für 4 Stunden auf 45 °C erwärmt.Then the phenol / triethylamine solution was transferred to the dropping funnel. The phenol / triethylamine solution was added dropwise to the well-cooled toluene / phosphorus trichloride solution with vigorous stirring within 4 h. Attention was paid to a constant dropping speed of one drop per second. The mixture was then warmed to room temperature and stirred for 12 hours, then heated to 45 ° C for 4 hours.
Zur Aufarbeitung wurde das entstandene Triehtylaminhydrochlorid abfiltriert und mit 20 ml getrocknetem Toluol nachgewaschen, das Filtrat wurde unter vermindertem Druck bis zur Trockene eingeengt.For workup, the resulting Triehtylaminhydrochlorid was filtered off and washed with 20 ml of dried toluene, the filtrate was concentrated to dryness under reduced pressure.
Masse: 41,5 g (Ausbeute 82%)Mass: 41.5 g (yield 82%)
12.0 g Bi-(2,4-di-tert.-butylphenyl)-chlorophopshit (0.021 mol) wurden in einem 250 ml Schlenkkolben in 100 ml getrocknetem Acetonitril gelöst.12.0 g of bi- (2,4-di-tert-butylphenyl) chlorophosphite (0.021 mol) were dissolved in 100 ml of dried acetonitrile in a 250 ml Schlenk flask.
In einen zweiten Schlenkkolben (250 ml) wurden 3,2 g (0,009 mol) 3,3'-Di-tert.-butyl-5,5'-dimethoxy-[1,1'-biphenyl]-2,2'diol unter Rühren zu 50 ml getr. Acetonitril und 2,2 g entgastes N,N-Dimethylaminobutan (DMAB) gegeben. Dabei entstand eine Suspension.Into a second Schlenk flask (250 ml) was added 3.2 g (0.009 mol) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'-biphenyl] -2,2'-diol with stirring to 50 ml drink. Acetonitrile and 2.2 g of degassed N, N-dimethylaminobutane (DMAB). This resulted in a suspension.
Dann wurde innerhalb einer 1 h die Biphenol/DMAB-Lösung bei 0 °C zur Chlorophosphitlösung getropft. Anschließend wurde diese über Nacht auf Raumtemperatur erwärmt und dann für 12 Stunden bei 55 °C gerührt. Anschließend wurde die Reaktionslösung wieder auf Raumtemperatur abgekühlt und abfiltriert. Der Feststoff wurde zweimal mit je 20 ml getrocknetem Acetonitril gewaschen und dann unter vermindertem Druck getrocknet und analysiert.The biphenol / DMAB solution was then added dropwise at 0 ° C. to the chlorophosphite solution over the course of 1 h. It was then warmed to room temperature overnight and then stirred for 12 hours at 55 ° C. Subsequently, the reaction solution was cooled again to room temperature and filtered off. The solid was washed twice with 20 ml each of dried acetonitrile and then dried under reduced pressure and analyzed.
Um das Produkt vom Tris(2,4-di-tert-butylphenyl)phosphit zu trennen, wurde der Feststoff von der Fritte in einem 500 ml Schlenkkolben umgefüllt, und mit 400 ml getrocknetem Acetonitril versetzt. Anschließend wurde der Schlenkkolben für 5 h auf 60 °C erwärmt, heiß filtriert und einmal mit 20 ml getrocknetem Acetonitril nachgewaschen.To separate the product from tris (2,4-di-tert-butylphenyl) phosphite, the solid was transferred from the frit in a 500 ml Schlenk flask and 400 ml of dried acetonitrile were added. Subsequently, the Schlenk flask was heated to 60 ° C for 5 h, filtered hot and washed once with 20 ml of dried acetonitrile.
Das Filtrat wurde unter vermindertem Druck eingeengt und analysiert.The filtrate was concentrated under reduced pressure and analyzed.
Um das Produkt weiter aufzureinigen, wurde der Schlenkkolben mit 80 ml getrocknetem Acetonitril versetzt und die Suspension wurde für 1,5 h auf 60 °C erwärmt und dann heiß gefrittet. Danach wurde das Filtrat unter vermindertem Druck eingeengt.To further purify the product, the Schlenk flask was treated with 80 ml of dried acetonitrile and the suspension was heated to 60 ° C. for 1.5 h and then hot-fritted. Thereafter, the filtrate was concentrated under reduced pressure.
Um das Amiohydrochlorid zu entfernen, wurde der Feststoff in 20 ml getrocknetem Toluol gelöst, 1/2 h bei Raumtemperatur gerührt und anschließend filtriert. Der Feststoff wurde 2 mal mit 10 ml getrocknetem Toluol nachgewaschen. Anschließend das Filtrat mittels vermindertem Druck eingeengt und analysiert.To remove the amiohydrochloride, the solid was dissolved in 20 mL of dried toluene, stirred for 1/2 h at room temperature and then filtered. The solid was washed twice with 10 ml of dried toluene. Then the filtrate is concentrated by means of reduced pressure and analyzed.
Masse: 3.2 g (26.7 % Ausbeute)Mass: 3.2 g (26.7% yield)
In einem 100 ml-Autoklaven der Fa. Parr Instruments wurde mit Hilfe von Synthesegas (CO/H2 = 1:1 (Vol-%)) Raffinat 3 hydroformyliert. Raffinat 3 ist ein Gemisch aus: ca. 26% 1-Buten, 32% trans-2-Buten, 17% cis-2-Buten, 25% n-Butan und Spuren an Iso-Butan und Neo-Pentan. Als Precursor wurden Rh(acac)(CO)2 in Toluol vorgelegt. Der Ligand wurde im molaren Überschüssen von 4:1 relativ zum Rhodium verwendet. Als Stabilisator wurde Tinuvin 770DF im molaren Verhältnis ca. 1:1 zum Liganden eingesetzt. Zusätzlich wurden als GC-Standard ca. 0.5 g Tetraisopropylbenzol (TIPB) zugefügt. Ca. 9 g Edukt wurden nach Erreichen der vorgesehenen Reaktionstemperatur zudosiert.In a 100 ml autoclave from Parr Instruments, raffinate 3 was hydroformylated with the aid of synthesis gas (CO / H 2 = 1: 1 (vol.%)). Raffinate 3 is a mixture of: about 26% 1-butene, 32% trans-2-butene, 17% cis-2-butene, 25% n-butane and traces of iso-butane and neo-pentane. The precursors were Rh (acac) (CO) 2 in toluene. The ligand was used in molar excesses of 4: 1 relative to the rhodium. The stabilizer used was Tinuvin 770DF in a molar ratio of about 1: 1 to the ligand. In addition, about 0.5 g of tetraisopropylbenzene (TIPB) was added as the GC standard. Approximately 9 g of educt were metered in after reaching the intended reaction temperature.
Während der Reaktion wurde der Druck über eine Synthesegasregelung mit Massedurchflussmesser konstant gehalten. Die Rührerdrehzahl betrug 1200 min-1. Proben wurden aus der Reaktionsmischung nach 5 Stunden gezogen. Die Ergebnisse der Versuche sind in Tabelle 1 zusammengefasst.During the reaction, the pressure was kept constant via a mass flow metering synthesis gas control. The stirrer speed was 1200 min -1 . Samples were withdrawn from the reaction mixture after 5 hours. The results of the experiments are summarized in Table 1.
In einem 100 ml-Autoklaven der Fa. Parr Instruments wurde bei 128 °C und 43 bar Synthesegasdruck 8.8 g Raffinat 3 hydroformyliert. Als Precursor wurden Rh(acac)(CO)2 (100 ppm Rh) in 45 g Toluol vorgelegt. Als Ligand wurden 0.107 g Ligand in der Katalysatoransatzlösung eingesetzt. Als organisches Amin wurden 0.057 g Tinuvin 770DF, sowie 0.451 g TIPB als GC-Standard zugefügt. Das Edukt wurde nach Erreichen der vorgesehenen Reaktionstemperatur zudosiert.In a 100 ml autoclave from Parr Instruments, 8.8 g of raffinate 3 were hydroformylated at 128 ° C. and 43 bar synthesis gas pressure. The precursors were Rh (acac) (CO) 2 (100 ppm Rh) in 45 g of toluene. The ligand used was 0.107 g of ligand in the catalyst feed solution. As organic amine, 0.057 g of Tinuvin 770DF and 0.451 g of TIPB as GC standard were added. The educt was metered in after reaching the intended reaction temperature.
Während der Reaktion wurde der Druck über eine Synthesegasregelung mit Massedurchflussmesser konstant gehalten. Proben wurden aus der Reaktionsmischung nach 5 Stunden gezogen.During the reaction, the pressure was kept constant via a mass flow metering synthesis gas control. Samples were withdrawn from the reaction mixture after 5 hours.
In Tabelle 1 sind die Hydroformylierungsergebnisse von Raffinat 3 bei 43 bar Synthesgasdruck und 128 °C dargestellt.
Bei der Hydroformylierung gibt es die n/iso-Selektivitäte: das Verhältnis von linearem Aldehyd (= n) zu verzweigtem Aldehyd (= iso). Hierbei bedeutet die Regioselektivität bezüglich des n-Aldehyden, dass diese Menge an linearem Produkt gebildet wurde. Die restlichen Prozente entsprechen dann dem verzweigten Isomer. Bei einer Regioselektivität von 50% entstehen also n-Aldehyd und iso-Aldehyd zu gleichen Teilen.In the hydroformylation there is the n / iso-selectivity: the ratio of linear aldehyde (= n) to branched aldehyde (= iso). Here, the regioselectivity with respect to the n-aldehyde means that this amount of linear product was formed. The remaining percentages then correspond to the branched isomer. With a regioselectivity of 50%, n-aldehyde and iso-aldehyde are formed in equal parts.
Mit der erfindungsgemäßen Verbindung (1) konnte die Regioselektivität im Vergleich zum Vergleichsliganden (2) deutlich der 50%-Marke angenähert werden, welche für ein ausgeglichenes Verhältnis von n-Aldehyd und iso-Aldehyd steht.With the compound ( 1 ) according to the invention, the regioselectivity in comparison with the comparison ligand ( 2 ) could be clearly approached the 50% mark, which stands for a balanced ratio of n-aldehyde and iso-aldehyde.
Die durchgeführten Versuche belegen, dass die gestellten Aufgaben durch die erfindungsgemäße Verbindung (1) gelöst werden.The experiments carried out prove that the objects are achieved by the compound ( 1 ) according to the invention.
Claims (14)
- Compound of the formula (I):R1, R2, R3, R4 are selected from: -H, -(C1-C12)-alkyl,-O-(C1-C12)-alkyl,wherein the alkyl groups mentioned may be substituted as follows:
substituted -(C1-C12)-alkyl groups and substituted -(C1-C12)-alkoxy groups, depending on their chain length, may have one or more substituents; the substituents are mutually independently selected from -(C3-C12)-cycloalkyl, -(C3-C12)-heterocycloalkyl, -(C6-C20)-aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl, where at least one of the R1, R2, R3, R4 radicals is not -H. - Compound according to Claim 1,
where R2 and R4 are selected from: -(C1-C12)-alkyl, -O-(C1-C12)-alkyl. - Compound according to either of Claims 1 and 2,
where R2 is -O-(C1-C12)-alkyl. - Compound according to any of Claims 1 to 3,
where R4 is -(C1-C12)-alkyl. - Compound according to any of Claims 1 to 4,
where R2 is selected from: -Me, -tBu, -OMe. - Compound according to any of Claims 1 to 5,
where R2 is -OMe. - Compound according to any of Claims 1 to 6,
where R4 is selected from: -Me, -tBu. - Compound according to any of Claims 1 to 7,
where R4 is -tBu. - Complex according to the formula (II):R1, R2, R3, R4 are selected from: -H, -(C1-C12)-alkyl,-O-(C1-C12)-alkyl,wherein the alkyl groups mentioned may be substituted as follows:substituted -(C1-C12)-alkyl groups and substituted -(C1-C12)-alkoxy groups, depending on their chain length, may have one or more substituents; the substituents are mutually independently selected from -(C3-C12)-cycloalkyl, -(C3-C12)-heterocycloalkyl, -(C6-C20)-aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl;where at least one of the R1, R2, R3, R4 radicals is not -H,and M is selected from: Rh, Ru, Co, Ir.
- Complex according to the formula (III):R1, R2, R3, R4 are selected from: -H, -(C1-C12)-alkyl,-O-(C1-C12)-alkyl,wherein the alkyl groups mentioned may be substituted as follows:substituted -(C1-C12)-alkyl groups and substituted -(C1-C12)-alkoxy groups, depending on their chain length, may have one or more substituents; the substituents are mutually independently selected from -(C3-C12)-cycloalkyl, -(C3-C12)-heterocycloalkyl, -(C6-C20)-aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl;where at least one of the R1, R2, R3, R4 radicals is not -H,and M is selected from: Rh, Ru, Co, Ir.
- Complex according to Claim 10 or 11,
where M = Rh. - Use of a compound according to Claims 1 to 9,
in a ligand-metal complex for catalysis of a hydroformylation reaction. - Process comprising the following process steps:a) initially charging an olefin,b) adding a complex according to either of Claims 10 and 11,
or a compound according to any of Claims 1 to 9 and a substance including a metal selected from: Rh, Ru, Co, Ir,c) feeding in H2 and CO,d) heating the reaction mixture, wherein the olefin is converted to an aldehyde.
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ES16197715T ES2746318T3 (en) | 2016-11-08 | 2016-11-08 | Bisphosphites with 2,4-tert-butylphenyl units and their use as ligands in hydroformylation |
EP16197715.2A EP3318569B1 (en) | 2016-11-08 | 2016-11-08 | Bis-phosphites with 2,4-tert. butylphenyl units and their use as ligands in the hydroformylation |
MYPI2017704176A MY178198A (en) | 2016-11-08 | 2017-11-02 | Bisphosphites having 2,4-tert-butylphenyl units and use thereof as ligands in hydroformylation |
TW106138090A TWI665210B (en) | 2016-11-08 | 2017-11-03 | Bisphosphites having 2,4-tert-butylphenyl units and use thereof as ligands in hydroformylation |
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KR1020170147015A KR102015458B1 (en) | 2016-11-08 | 2017-11-07 | Bisphosphites having 2,4-tert-butylphenyl units and use thereof as ligands in hydroformylation |
US15/805,401 US10526356B2 (en) | 2016-11-08 | 2017-11-07 | Bisphosphites having 2,4-tert-butylphenyl units and use thereof as ligands in hydroformylation |
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